Soluble carob

ABSTRACT

The invention concerns a gum carob with average mole weight (Mw) ranging between 2.5.105 and 1.5.106 g/mol and whereof at least 60 wt. % of said gum is soluble in an aqueous medium at a temperature not higher than 60° C.

[0001] The present invention relates to a carob bean gum (or locust beangum) having a weight-average molecular mass ({overscore (M)}_(w)) ofbetween 2.5×10⁵ and 1.5×10⁶ g/mol, at least 60% by weight of said gumbeing soluble in an aqueous medium at a temperature equal to or lessthan 60° C., to its method of preparation and to its use.

[0002] It also relates to a gelling composition comprising said carobbean gum and at least one hydrocolloid.

[0003] Various industries, such as the cosmetics, dyeing, food, oil andcleaning products industries, seek texture agents that modify theTheological properties of liquid phases, especially aqueous phases.

[0004] The rheology of aqueous phases is usually modified by glucidederivatives of plant or animal origin.

[0005] The choice of these glucide derivatives depends, for example, ontheir cost, their availability, the conditions under which they may beused and the types of compounds in which they may be suitable.

[0006] Thus, galactomannans, which are nonionic polysaccharidesextracted from the albumen of seeds of leguminous plants of which theyconstitute the storage carbohydrate, are often employed as textureagents.

[0007] Among galactomannans most often employed, mention may be made ofcarob bean gum. This is extracted from the seeds of the carob tree(Ceratonia siliqua L.) which is a tree with persistent foliageoriginally from Syria and Asia Minor, but cultivated along the entireMediterranean littoral.

[0008] Carob bean gum is composed of a main chain consisting ofD-mannopyranose units linked in the β(1-4) position, carrying sidebranches consisting of a single D-galactopyranose unit in the α(1-6)position.

[0009] Carob bean gum is in general known for its texturing propertiesand more particularly for its thickening and stabilizing properties.

[0010] It is more particularly beneficial as, because of its nature, itis compatible with other compounds, especially hydrocolloids, andtherefore can be used in combination with these to produce synergisticeffects in terms of texture. For example, in combination with xanthangum or carragheenans, gels of different strength and greater or lesserelastic consistency may be obtained.

[0011] However, in aqueous medium, native carob bean gum exhibitssatisfactory solubility, that is to say greater than 60% by weight ofthe gum, only at temperatures above 80° C.

[0012] Thus, for practical and economic reasons, industrial concerns arecurrently seeking more and more to replace native carob bean gum withcarob bean gums that have better solubility at temperatures below theusual temperatures for dissolving native carob bean gums.

[0013] The object of the present invention is to provide a carob beangum having properties similar to those of native carobs (for example interms of texturing, compatibility with other compounds, etc.) and goodsolubility at temperatures well below the usual temperatures fordissolving native carob bean gums.

[0014] The object of the invention is also to provide a carob bean gumwhich, at a constant concentration, allows a variable viscosity range tobe achieved.

[0015] For this purpose, one subject of the present invention is a carobbean gum having a weight-average molecular mass ({overscore (M)}_(w)) ofbetween 2.5×10⁵ and 1.5×10⁶ g/mol, at least 60% by weight of said gumbeing soluble in an aqueous medium at a temperature equal to or lessthan 60° C.

[0016] Another subject of the invention is a method of preparing thecarob bean gum of the above type.

[0017] Yet another subject of the invention is gelling compositionscomprising the carob bean gum of the above type and at least onehydrocolloid.

[0018] Finally, the invention relates to food formulations comprisingthe abovementioned gelling compositions.

[0019] Within the context of the present invention, the expression“solubility in an aqueous medium at a temperature equal to or less than60° C.” means that at a temperature equal to or less than 60° C., in anaqueous medium, the carob bean gum develops 60% of the viscosity that itwould have developed if it had been dissolved at temperatures above 80°C.

[0020] Within the meaning of the invention, “aqueous medium” denotes amedium which consists partly of water.

[0021] Thus, the subject of the invention is firstly a carob bean gumhaving a weight-average molecular mass ({overscore (M)}_(w)) of between2.5×10⁵ and 1.5×10⁶ g/mol, at least 60% by weight of said gum beingsoluble in an aqueous medium at a temperature equal to or less than 60°C.

[0022] Under these temperature conditions, the solubility of the gumaccording to the invention may advantageously be at least 70% by weight,and preferably be at least 80% by weight, of said gum.

[0023] These solubility levels—that is to say at least 60% by weight,advantageously at least 70% by weight and preferably at least 80% byweight of the gum—may be achieved more particularly at temperature oneless than 60° C., advantageously between 10° C. and 45° C. andpreferably between 15° C. and 30° C.

[0024] In a preferred embodiment of the invention, these solubilitylevels are achieved at a temperature that may vary from 20° C. to 25° C.

[0025] The weight-average molecular mass ({overscore (M)}_(w)) of thegum according to the invention is advantageously between 2.5×10⁵ and1×10⁶ g/mol and preferably between 2.5×10⁵ and 6×10⁵ g/mol.

[0026] It may be measured by gel permeation chromatography (GPC). Inthis case, standard synthetic polymer solutions are used for thecalibration.

[0027] It may also be determined by light scattering.

[0028] The viscosity measurement may also give information about theweight-average molecular mass ({overscore (M)}_(w)). Thus at 25° C. a 1%aqueous solution of the carob bean gum according to the invention has aviscosity of between 15 and 2000 mPa.s (measured at 20 rpm). Theviscosity of such a solution is preferably between 15 and 1000 mPa.s.

[0029] The viscosity may be measured using a Brookfield DV-IIIviscometer at 25° C. and 20 rpm.

[0030] The weight-average molecular mass ({overscore (M)}_(w)) of thecarob bean gum according to the invention is such that its intrinsicviscosity [η] is greater than 2.3 dl/g.

[0031] The relationship between the intrinsic viscosity [η] and theweight-average molecular mass ({overscore (M)}_(w)) can be obtained inthe following manner (A. Sabater de Sabates, 1979, Doctoral Thesis,University of Orsay, ENSIA, Massy, France):

[η]=1.24×10⁻⁴ ×{overscore (M)} _(w) ^(0.8)

[0032] This viscosity is measured by means of a U-shaped viscometer ofthe Ubbelhode type.

[0033] The D-mannopyranose/D-galactopyranose mass ratio (M/G) of thecarob according to the invention is between 1 and 5, preferably between2 and 4. Knowing this ratio constitutes one of the means ofcharacterizing the specimen, although it provides no information aboutthe statistical distribution of the D-galactopyranose branches along themain chain.

[0034] The carob bean gum having the aforementioned characteristics isobtained by reducing the weight-average molecular mass ({overscore(M)}_(w)) of the native gum. This reduction is in general obtained byscission of the glycosic bonds for the purpose of producing shorterchains which are substantially identical, from the chemical standpoint,to the native gum.

[0035] Reducing the weight-average molecular mass ({overscore (M)}_(w))gives the gum certain advantages. For example, it makes it possible toobtain a carob whose texturing properties, in particular its thickeningand stabilizing properties, may be adjusted. Furthermore, it allows acarob bean gum to be obtained which is capable of forming pseudo-gelsand/or having emulsifying properties, hence distinguishing it from thenative gum.

[0036] Another aspect of the invention is the method of preparing thecarob bean gum as described above.

[0037] This method comprises the following steps:

[0038] (i) the endosperm of the carob bean gum is hydrated;

[0039] (ii) the hydrated endosperm is simultaneously dried and ground;and

[0040] (iii) after step (ii), the weight-average molecular mass of thecarob is reduced by depolymerizing the latter.

[0041] In step (i), the hydration of the carob bean gum endosperm iscarried out for a time long enough to achieve a degree of hydration ofbetween 50 and 90%.

[0042] The degree of hydration may be calculated, for example, by simplymeasuring the solids content of the endosperm.

[0043] After step (ii), the carob is in the form of a powder with awater content which is advantageously between 6 and 12%.

[0044] The particle size of this powder may vary depending on theoperating conditions. For example, it may vary from 20 to 200 μm.

[0045] The particle size may be measured by laser diffraction, forexample using a Malvern Mastersizer® 2000 laser particle size analyzer.

[0046] The drying/grinding operation is more particularly carried out ata temperature of between 30° C. and 90° C.

[0047] This operation may be carried out in any type of apparatus forsimultaneous grinding and drying, such as for example a hammer mill orneedle mill.

[0048] The depolymerization of the carob may be carried out byoxidation, by an enzymatic process, or by acid hydrolysis, under theeffect of high temperature and pressure and in the presence of anoxidizing agent, or by physical treatment such as, for example, byexposure to gamma-type radiation.

[0049] Advantageously, the depolymerization is carried out by oxidation.The oxidation is preferably carried out in an alkaline medium in thepresence of an agent of the type belonging to the family of peroxides,such as peracetic acid, H₂O₂, etc.

[0050] The depolymerization reaction time depends on the finalweight-average molecular mass desired.

[0051] The depolymerization may be carried out in a reactor providedwith a mixing system suitable for handling fine powder, that is to saypowder with a particle size of around 20 to 200 μm, so as to prevent theformation of crumbs. As nonlimiting examples, mention may be made ofLödige-type reactors, and ribbon mixers.

[0052] After depolymerization, if necessary, the excess alkalinity maybe neutralized by adding, for example, ammonium hydroxide or an acid,such as acetic acid, citric acid, phosphoric acid or sulfuric acid.

[0053] The depolymerized carob may then be dried. This drying may becarried out in any type of apparatus that avoids the formation ofagglomerates. For example, a Turbosphere, a needle mill or a flash dryermay be used.

[0054] The final carob bean gum is preferably in the form of a powder.Its water content is advantageously between 6 and 12%.

[0055] The steps may be carried out in any order. However, they arepreferably carried out in the order indicated above.

[0056] The carob bean gum according to the invention havephysico-chemical characteristics compatible with the definitions of thecarob bean gum that are described in “Food Chemical Codex”, 4th edition,page 768 and in European Union (EU) Directive No. 98/86/CE of Nov. 11,1998.

[0057] The carob bean gum of the invention may be used as a textureagent, especially as thickeners, stabilizers, gelling agents (capable offorming pseudo-gels) and/or emulsifiers in the field of cosmetics, thedyeing and food industries, the oil industry and the field of cleaningproducts.

[0058] Said gum is intended more particularly for the food field.

[0059] In combination with other compounds, especially hydrocolloids,the carob bean gum of the present invention may form a gel whosephysical properties (melting point, gel strength, etc.) may becontrolled.

[0060] At this stage, it is appropriate to define the term “gel”. Withinthe context of the present invention, by the term “gel” is meant apseudo-solid (behavior approaching that of a solid) resulting from theat least partial combination of polysaccharide chains dispersed in aliquid. Within a range of stressing frequencies ω, pseudo-solid gels arein general characterized as regards their solid component by an elasticmodulus G′(ω), also called the storage modulus, and as regards theirliquid or viscous component by a viscous modulus G″(ω) also called theloss modulus.

[0061] The mechanical quantities G′(ω) and G″(ω) may be measured usingan imposed-strain rheometer operating in oscillatory mode. As anindicative and nonlimiting example, mention may be made of a Rheo-FluidSpectrometer® rheometer.

[0062] G′(ω) and G″(ω) may also be measured using an imposed-stressrheometer operating in oscillatory mode. As an indicative example,mention may be made of a AR1000® rheometer (from TA Instruments).

[0063] The principle of the measurement consists in determining firstlythe range of reversible mechanical strain in which the response of thegel to the mechanical stress as a function of said strain is linear.Secondly, the gel is subjected to a fixed value of mechanical strainwithin the linear range determined above. The rheometer then performs anω frequency sweep.

[0064] That stress response of the gel which is in phase with the strainenables the elastic modulus G′(ω) to be obtained. G′(ω) corresponds tothe energy stored by the gel in elastic form, this energy beingrecoverable.

[0065] That stress response of the gel which is out of phase by an angleof 90° with the strain enables the viscous modulus G″(ω) to be obtained.G″(ω) corresponds to the energy dissipated by viscous flow, this energybeing nonrecoverable.

[0066] A gel is called a true gel when, over the entire range of sweptstressing frequencies (ω), the G′/G″ ratio is greater than or equal to10 and when the value of G′(ω) is greater than or equal to 10 Pa.

[0067] Likewise, a gel is called a pseudo-gel when, over the entirerange of swept stressing frequencies (ω), the G′/G″ ratio is greaterthan or equal to 5 and when the value of G′(ω) is greater than or equalto 1 Pa.

[0068] Another aspect of the present invention relates to gellingcompositions comprising carob bean gum according to the invention withat least one hydrocolloid.

[0069] Completely unexpectedly, it has been found that the carob beangum of the invention by itself or in combination with at least onehydrocolloid can result in a pseudo-gel at a temperature equal to orless than 60° C. It has also been found that, as in the case of thenative carob bean gum, the combination of the carob of the inventionwith at least one hydrocolloid can give true gels by heating to atemperature equal to or greater than 80° C.

[0070] Among hydrocolloids, mention may be made by way of nonlimitingexample of xanthan gum, carragheenans, agar, Danish agar, and gellangum. Preferably, the hydrocolloid is xanthan gum.

[0071] In these compositions, the mass ratio of carob bean gum asdefined above to the hydrocolloid(s) is(are) chosen between 5/95 and95/5, advantageously between 20/80 and 80/20 and preferably between40/60 and 60/40.

[0072] According to one embodiment of the invention, this mass ratio is50/50.

[0073] These compositions may be obtained by simple mixing of thecomponents, namely the carob and the hydrocolloid or hydrocolloids. Thecomponents may be mixed in the form of powder and then dissolved. Theymay also be mixed in the form of solutions. It may also be envisioned toadd one of the components in powder form to the other component, whichis in solution. In the latter case, it is important to avoid theformation of agglomerates during mixing.

[0074] Furthermore, the invention relates to a method of gelling anaqueous phase, characterized in that a pseudo-gel is formed by theaddition of a gelling composition as defined above to said phase, at atemperature equal to or less than 60° C., more particularly less than60° C., advantageously between 10° C. and 45° C. and preferably between15° C. and 30° C., and after a sufficient rest time.

[0075] In a preferred embodiment of the invention, the addition of thegelling composition may be carried out at a temperature that may varyfrom 20° C. to 25° C.

[0076] It should be noted that in the preferred embodiment of theinvention, the addition of the gelling composition and the formation ofthe pseudo-gel take place at a temperature that may vary from 20° C. to25° C.

[0077] The invention also extends to the method of gelling an aqueousphase, characterized in that a true gel is formed by the addition of agelling composition as defined above to said phase, at a temperatureequal to or greater than 80° C., and [lacuna] a sufficient rest time.

[0078] Given that, to form a true gel, the addition of the gellingcomposition to the aqueous phase will take place at temperatures equalto or greater than 80° C., a cooling step will possibly be necessary.

[0079] A person skilled in the art is capable of determining thesuitable rest time depending on the desired G′(ω) and G″(ω) values.

[0080] Thus, it has been found that, for example, 1% weight/weightsolutions of the gelling composition in distilled water at 25° C., at afrequency of 1 Hz, lead to G′(ω) values of between 1 and 1000 Pa,preferably between 10 and 1000 Pa, with a G′/G″ ratio of greater than 5.

[0081] The amount of the gelling composition that can be used willdepend on the aqueous phase to be gelled. This amount may represent from0.01 to 10%, advantageously from 0.5 to 2% and preferably from 0.8 to1.5% by weight, of the gelled phase.

[0082] It does not matter whether the gelling composition is introducedin the form of a solid or in the form of an aqueous solution.

[0083] These gelling compositions may be used in the oil, agrochemical,food, paper and textile industries, as well as in paints and domestic orindustrial cleaning agents.

[0084] More particularly, the gelling compositions are intended for foodformulations.

[0085] Among the food formulations in which the use of such compositionsare suitable, mention may be made, for example, of compositions of thefollowing types: jellies, custards, cup custards, aspic, cold jelliedpoultry, bavaroises, yogurts, ice creams, sorbets, crèmes brûlées,drinks, etc.

[0086] Specific but nonlimiting examples of the invention will now begiven.

EXAMPLES

[0087] In the examples that follow, the intrinsic viscosity and theweight-average molecular mass ({overscore (M)}_(w)) are determined inthe following manner:

[0088] Measurement of the Intrinsic Viscosity

[0089] A 1% weight/weight solution of the carob according to theinvention is prepared by vigorous stirring in demineralized water. Thesolution is then left to stand at about 25° C. for 24 h. By centrifugingfor 1 h at 14 000 rpm, the supernatant liquid is recovered and filteredon glass wool. This mother liquor is then used to prepare solutions oflower concentrations by dilution in demineralized water.

[0090] The reduced viscosities, and then specific viscosities, are thencalculated at 25° C. with a U-shaped viscometer of the Ubbelhode type bymeasuring the drop times.

[0091] Finally, the intrinsic viscosities [η] are determined byextrapolation to zero concentration:

[0092] either by the Huggins method, by plotting the “specificviscosity/concentration” curve as a function of concentration;

[0093] or by the Kraemer method, by plotting the “natural logarithm ofthe reduced viscosity)/concentration” curve as a function ofconcentration. The two methods give the same result.

[0094] Measurement of the Weight-Average Molecular Mass

[0095] The weight-average molecular mass is determined by gel permeationchromatography using polyethylene oxide standard solutions ascalibration standards.

Example 1 Preparation of a Carob Bean Gum According to the Invention

[0096] By following steps (i) to (iii) of the process described in thetext (depolymerization by alkaline oxidation in the presence of sodiumhydroxide NaOH and hydrogen peroxide H₂O₂; neutralization with aceticacid CH₃CO₂H; reaction time of 100 minutes at 70° C.) in the orderindicated, a carob bean gum having the following characteristics wasobtained:

[0097] water content: 11.2%;

[0098] Brookfield viscosity at 25° C. and 20 rpm of a 2% weight/weightsolution in demineralized water:

[0099] after 24 h and dissolved at 25° C.: 150 mPa.s,

[0100] after 24 h and dissolved at 80° C.: 190 mPa.s, hence a solubilityof 79%;

[0101] intrinsic viscosity: [Λ]=3.7 dl/g;

[0102] weight-average molecular mass: {overscore (M)}_(w)=4.5×10⁵ g/mol;and

[0103] equilibrium surface tension of a 0.5% weight/weight solution indistilled water: γ=39 mN/m (measured at 25° C. by means of a drop volumetensiometer of the LAUDA TVT 1 type).

Example 2 Comparative Example Preparation of Only Depolymerized CarobBean Gum

[0104] By carrying out only step (iii) of depolymerizing a native carobbean gum, without passing through steps (i) and (ii) prior todepolymerization, a carob bean gum having a viscosity, after beingdissolved at a temperature greater than or equal to 80° C., similar tothe carob bean gum of example 1 was obtained. However, the level ofsolubility of this gum was substantially less than 60% by weight. Thisgum had the following characteristics:

[0105] the Brookfield viscosity at 25° C. and 20 rpm of a 2%weight/weight solution in demineralized water:

[0106] after 24 h and dissolved at 25° C.: 57 mPa.s,

[0107] after 24 h and dissolved at 80° C.: 243 mPa.s, hence a solubilityof 23%.

Example 3 Gelling Composition According to the Invention

[0108] The gelling composition of example 3 was prepared by mixing, in a50/50 weight ratio, the following two powders: the carob bean gum ofexample 1 and xanthan gum (RHODIGEL™ 200 sold by Rhodia).

[0109] After dissolving this gelling composition by vigorous stirringfor 10 minutes in an aqueous medium at 25° C. and after a rest time of24 h at a temperature of around 25° C., pseudo-gels having the followingcharacteristics were obtained:

[0110] for a total concentration of gelling composition of 1%weight/weight in demineralized water, the moduli G′(ω) and G″(ω) were 40and 8 Pa, respectively;

[0111] for a total concentration of gelling composition of 1%weight/weight in skimmed milk (10% weight/weight solution of powderedskimmed milk in demineralized water), the moduli G′(ω) and G″(ω) were100 and 20 Pa, respectively.

[0112] For the same gelling composition, after being dissolved byvigorous stirring for 10 minutes in an aqueous medium at a temperaturegreater than or equal to 80° C., and after a rest time of 24 h at atemperature of around 25° C., true gels were obtained with the followingcharacteristics (total concentration of gelling composition of 1%weight/weight in a 1% weight/weight KCl solution):

[0113] the moduli G′(ω) and G″(ω) were 140 and 7 Pa, respectively;

[0114] the gelling and melting temperatures were 54° C. and 56° C.respectively (these temperatures were determined at the point ofintersection of the G′ and G″ versus temperature curves; variation at−2° C./min in the case of gelling and at +2° C./min in the case ofmelting, within the reversible mechanical deformation range of the gel,at a frequency of 1 Hz); and

[0115] the strength of the gel for a depth of penetration of 10 mm was80 g/cm² (determined using a texturometer of the TA-XT2® type for a rateof penetration of the piston of 0.5 mm/s; cylinder of 1 cm² crosssection).

[0116] As a comparison, by following the same operating method asdescribed above (by dissolving the powder mixture with vigorous stirringfor 10 minutes in an aqueous medium at a temperature equal to or greaterthan 80° C.; rest time of 24 h at a temperature of around 25° C.), truegels were obtained with a native carob (MEYPRO-FLEUR™ 200, sold byMeyhall AG)/xanthan gum (RHODIGEL™ T 200, sold by Rhodia) mixture (50/50weight ratio), said true gels having the following characteristics(total concentration of gums of 1%. weight/weight in a 1% weight/weightKCl solution):

[0117] the moduli G′(ω) and G″(ω) were 200 and 10 Pa, respectively;

[0118] the gelling and melting temperatures were 62° C. and 67° C.,respectively; and

[0119] the strength of the gel for a depth of penetration of 10 mm was83 g/cm².

[0120] It may therefore be seen that the interaction between the carobbean gum of the invention and the xanthan gum is greatly favoredcompared with the native carob bean gum (this is because, for the sameamount of carob bean gum according to example 1 and of the native carobbean gum, the same gel strength is obtained, whereas the Brookfieldviscosity developed by the native carob bean gum is appreciably higher:3000 mPa.s at a concentration of 1% weight/weight; dissolved at atemperature above 80° C.; Brookfield viscosity measured at 25° C. and 20rpm).

Example 4 Use of a Gelling Composition in Custard-Type Food Formulations

[0121] Vanilla Custard Ingredients Sugar 12.0% Gelling composition⁽¹⁾ 0.80% Vanilla flavoring  0.05% Coloring agent  0.05% NaCl  0.02%Semiskimmed milk the balance to 100%

[0122] Recipe

[0123] Mix the gelling composition with the other dry ingredients;

[0124] Heat the milk to 85° C.;

[0125] Introduce the powder mixture and stir at 85° C. for 15 minutes at1000 rpm;

[0126] Leave to cool and stand overnight in a refrigerator at 4° C.=6°C.

[0127] Characterization of the Custard

[0128] An elastic gel was obtained, with a moderate gel strength (30g/cm² at 10 mm) and suitable organoleptic qualities.

[0129] If in the gelling composition the carob bean gum of example 1were to be replaced with native carob bean gum, a firmer custard, lesspleasant in one's mouth, was obtained.

1. A carob bean gum having a weight-average molecular mass ({overscore(M)}_(w)) of between 2.5×10⁵ and 1.5×10⁶ g/mol, at least 60% by weightof said gum being soluble in an aqueous medium at a temperature equal toor less than 60° C.
 2. The carob bean gum as claimed in claim 1,characterized in that the solubility of the gum according to theinvention is at least 70% by weight, and preferably at least 80% byweight, of said gum.
 3. The carob bean gum as claimed in either ofclaims 1 and 2, characterized in that the solubility levels—that is tosay at least 60% by weight, advantageously at least 70% by weight andpreferably at least 80% by weight of the gum—are achieved moreparticularly at a temperature less than 60° C., advantageously between10° C. and 45° C. and preferably between 15° C. and 30° C.
 4. The carobbean gum as claimed in the preceding claim, characterized in that thesolubility levels are achieved at a temperature varying from 20 to 25°C.,
 5. The carob bean gum as claimed in any one of claims 1 to 4,characterized in that it has a weight-average molecular mass ({overscore(M)}_(w)) of between 2.5×10⁵ and 1×10⁶ g/mol.
 6. The carob bean gum asclaimed in claim 5, characterized in that it has a weight-averagemolecular mass ({overscore (M)}_(w)) of between 2.5×10⁵ and 6×10⁵ g/mol.7. A method of preparing a carob bean gum as claimed in any one ofclaims 1 to 6, comprising the following steps: (i) the endosperm of thecarob bean gum is hydrated; (ii) the hydrated endosperm issimultaneously dried and ground; and (iii) after step (ii), theweight-average molecular mass of the carob is reduced by depolymerizingthe latter.
 8. The method as claimed in claim 7, characterized in thatin step (i), the hydration of the carob bean gum endosperm is carriedout for a time long enough to achieve a degree of hydration of between50 and 90%.
 9. The method as claimed in either of claims 7 and 8,characterized in that after step (ii), the carob is in the form of apowder with a water content which is advantageously between 6 and 12%.10. The method as claimed in any one of claims 7 to 9, characterized inthat the drying/grinding operation is carried out at a temperature ofbetween 30° C. and 90° C.
 11. The method as claimed in any one of claims7 to 10, characterized in that the depolymerization of step (iii) iscarried out by oxidation.
 12. A carob bean gum having a weight-averagemolecular mass ({overscore (M)}_(w)) of between 2.5×10⁵ and 1.5×10⁶g/mol, at least 60% by weight of said gum being soluble in an aqueousmedium at a temperature equal to or less than 60° C., obtained by themethod as claimed in any one of claims 7 to
 11. 13. The use of a carobbean gum as claimed in any one of claims 1 to 6 and 12, as thickeners,stabilizers, gelling agents (capable of forming pseudo-gels) and/oremulsifiers in the field of cosmetics, the dyeing and food industries,the oil industry and the field of cleaning products.
 14. A gellingcomposition comprising carob bean gum as claimed in any one of claims 1to 6 and 12 with at least one hydrocolloid.
 15. The gelling compositionas claimed in the preceding claim, characterized in that thehydrocolloids is chosen from xanthan gum, carragheenans, agar, Danishagar, and gellan gum.
 16. The gelling composition as claimed in eitherof claims 14 and 15, characterized in that the mass ratio of carob beangum to the hydrocolloid(s) is between 5/95 and 95/5, advantageouslybetween 20/80 and 80/20 and preferably between 40/60 and 60/40.
 17. Thegelling composition as claimed in claim 16, characterized in that themass ratio of the carob bean gum to the hydrocolloid(s) is 50/50.
 18. Amethod of gelling an aqueous gelling phase, characterized in that apseudo-gel is formed by the addition of a gelling composition as claimedin any one of claims 14 to 17 to said phase, at a temperature equal toor less than 60° C., more particularly less than 60° C., advantageouslybetween 10° C. and 45° C. and preferably between 15° C. and 30° C., andafter a sufficient rest time.
 19. The method of gelling an aqueous phaseas claimed in the preceding claim, characterized in that a pseudo-gel isformed by the addition of a gelling composition as claimed in any one ofclaims 14 to 17 to said phase, at a temperature varying from 20° C. to25° C.
 20. A method of gelling an aqueous phase, characterized in that atrue gel is formed by the addition of a gelling composition as claimedin any one of claims 14 to 17 to said phase, at a temperature equal toor greater than 80° C., and [lacuna] a sufficient rest time.
 21. The useof a gelling composition as claimed in any one of claims 14 to 17, inthe oil, agrochemical, food, paper and textile industries, as well as inpaints and domestic or industrial cleaning agents.
 22. The use of agelling composition as claimed in any one of claims 14 to 17, in foodformulations of the following types: jellies, custards, cup custards,aspic, cold jellied poultry, bavaroises, yogurts, ice creams, sorbets,crèmes brûlées, drinks.